Visible light and fulvic acid assisted generation of Mn(III) to oxidize bisphenol A: The effect of tetrabromobisphenol A

Bisphenol A (BPA) and tetrabromobisphenol A (TBBPA), endocrine disrupting compounds (EDCs), are of increasing concerns for many years. This paper presents the elimination of BPA under visible light (VL) (λ ≥ 420 nm) irradiated solutions containing fulvic acid (FA) and MnSO4 (Mn(II)), and examines the possible effects of TBBPA on the transformation of BPA. After 72 h of reaction time, the removal efficiency of BPA in the studied system was 69%. Results of different experiments to identify oxidative species suggested the dominate role of soluble manganese (III) (Mn(III)) in the conversion of BPA. The transformation of BPA by the VL/FA/Mn(II) system was through self-oligomerization in absence of co-existence of TBBPA. In the co-existence of BPA with TBBPA, the removal of BPA was largely inhibited due to the competition with available Mn(III) and the possible occurrence of cross-coupling reactions between the two EDCs. This phenomenon was further elucidated by product analyses and density functional theory (DFT) calculations. The energy difference (ΔE) for generating a cross-coupling product was calculated as -23.4 kJ mol-1, much lower than the positive values of ΔE for self-coupling products of BPA or TBBPA, demonstrating that cross-coupling reactions between BPA and TBBPA likely occurred easier than the respective self-coupling reactions. The toxicity test showed that the overall estrogenic activity of BPA reaction solution was significantly decreased by the VL/FA/Mn(II) system. In general, our study provided new insights into the transformation of co-existing EDCs by in situ formed Mn(III) in aqueous solution.